This invention is in the field of fluoromonomer polymerization using chain transfer agents.
In its simplest form, free-radical polymerization begins with the reaction of a free radical, generated by an initiator, with an olefin molecule to form a new free radical. This adds in turn to another olefin molecule in a polymerization cycle which continues until the growing radical chain is terminated by coupling or disproportionation with another radical chain, or by reaction with an initiator-generated radical. The rate of termination compared with the rate of polymerization affects the molecular weight and molecular weight distribution of the polymer, both critical properties. Because these termination mechanisms do not always give desirable molecular weights or molecular weight distributions and sometimes produce polymer molecules with unstable endgroups or bonds, chain transfer agents are often included in polymerization recipes. See for example U.S. Pat. Nos. 3,636,926 and 5,700,889. Chain transfer agents are molecules with labile atoms, often hydrogen. They give up the labile atom to a growing polymer chain, terminating it. In the process the chain transfer agent is converted to a free radical which initiates a new polymer chain by reacting with an olefin molecule, starting a new polymerization cycle. Chloroform is an example:
xe2x80x83(polymer)xc2x7+HCCl3xe2x86x92(polymer)xe2x80x94H+xc2x7CCl3 growing chain terminated xc2x7CCl3+olefinxe2x86x92Cl3C-monomerxc2x7
Though effective in fluoromonomer polymerization, chloroform has undesirable health and environmental effects. Hydrocarbons, such as ethane, are also used as chain transfer agents, and are free of the problems of chloroform. However, ethane is a gas. Many fluoromonomers are also gases, and polymerizations often include the recycling of monomers. The presence of chain transfer agents such as ethane in monomer recycle streams presents problems of analysis and purification that increase costs and the probability of contamination. Liquid hydrocarbons are unsuitable because to achieve low enough volatility so that they do not have-a significant concentration in the gas phase, their molecular weights must be high. Fluoropolymers made with high molecular weight hydrocarbon chain transfer agents would have hydrocarbon end groups that would affect their properties and stability.
New chain transfer agents are needed that do not contain chlorine, are liquid at room temperature, and do not significantly affect the character of the polymer being made.
The present invention provides a chain transfer agent that is chlorine-free, liquid at room temperature, and similar in chemical composition to fluoropolymers made with them, that the fluoropolymer properties are not adversely affected. Thus the invention is a process comprising the polymerizing of fluoromonomer in the presence of initiator and chain transfer agent, said chain transfer agent having the formula
R1xe2x80x94Oxe2x80x94R2xe2x80x83xe2x80x83(1)
wherein R1 is a straight chain or branched saturated hydrocarbon group of 1 to 6 carbon atoms with the proviso that there is at least one hydrogen atom attached to the carbon next to oxygen, and R2 is a straight chain or branched fluorocarbon group or hydrofluorocarbon group of formula CaHbFc wherein a is 2 to 6, b is 0 to 2axe2x88x921 and c is 2 to 2a+1 with the proviso that b+c=2a+1.
Another aspect of the invention is polymer containing endgroups characteristic of chain transfer agent having the formula (1)
R1xe2x80x94Oxe2x80x94R2xe2x80x83xe2x80x83(1)
wherein R1 and R2 are as defined above.
Olefins are molecules containing a carbon-carbon double bond ( greater than Cxe2x95x90C less than ). The vinyl group (CH2xe2x95x90CHxe2x80x94) is a member of the class of olefins. xe2x80x9cFluoromonomersxe2x80x9d is used in this application to mean olefins that can be free-radically polymerized and that contain at least one fluorine atom, fluoroalkyl group, or fluoroalkoxy group attached to the vinyl group that undergoes polymerization. Useful fluoromonomers include, but are not limited to, vinyl fluoride; vinylidene fluoride; trifluoroethylene; chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene. (TFE); hexafluoropropylene (HFP); perfluoro(alkyl vinyl ethers). such as perfluoro(methyl vinyl ether)(PMVE), perfluoro(ethyl vinyl ether)(PEVE), and perfluoro(propyl vinyl ether)(PPVE); perfluoro(1,3-dioxole); perfluoro(2,2-dimethyl-1,3-dioxole) (PDD); CF2xe2x95x90CFOCF2CF(CF3)OCF2CF2X wherein X is SO2F, CO2H, CO2CH3, CH2OH, CH2OCN or CH2OPO3H; CF2xe2x95x90CFOCF2CF2SO2F; F(CF2)nCH2OCFxe2x95x90CF2 wherein n is 1, 2, 3, 4, or 5; R4CH2OCF=CF2 wherein R4 is hydrogen or F(CF2)mxe2x80x94 and m is 1, 2 or 3; and R5OCFxe2x95x90CH2 wherein R5 is F(CF2)zxe2x80x94 and z is 1, 2, 3, or 4; perfluorobutyl ethylene (PFBE); 3,3,3-trifluoropropene and 2-trifluoromethyl-3,3,3-trifluoro-1-propene. Preferred fluoromonomers include 2-trifluoromethyl-3,3,3-trifluoro-1-propene, PFBE, vinyl fluoride, vinylidene fluoride, TFE, HFP, PMVE, PEVE, PPVE, CTFE, and PDD.
The fluoromonomer may be polymerized alone to form a homopolymer if the fluoromonomer can be homopolymerized, or may be polymerized with one or more other fluoromonomers or other monomers, such as hydrocarbon monomers that are not fluoromonomers, to form a copolymer. If a copolymer is to be formed, the monomers chosen must be able to copolymerize. Fluorine-free monomers that copolymerize with some combinations of fluoromonomers include propylene and ethylene. Examples of useful homopolymers from fluoropolymers include polytetrafluoroethylene (PTFE) and polyvinylidene fluoride. Also usually classed with homopolymer PTFE are the modified PTFE polymers containing fluoromonomers other than TFE in such minor amounts that the modified polymers retain the non-melt-fabricable character of PTFE. Examples of useful copolymers include the copolymers of TFE with HFP and/or perfluoro(alkyl vinyl ethers) such as PPVE or PEVE, copolymers of TFE with PMVE, copolymers of TFE with PDD, and copolymers of TFE or CTFE with ethylene. Further examples include the copolymers of vinylidene fluoride with HFP, or with HFP and TFE. As implied above, copolymers may contain additional monomers beyond those named. TFE/ethylene copolymers, for example, are most useful if they include additional monomers that introduce bulky side groups such as PFBE, HFP, PPVE or 2-trifluoromethyl-3,3,3-trifluoro-1-propene, and elastomeric polymers frequently include low concentrations of cure site moieties derived from a cure site monomer.
The polymers of this invention include TFE and CTFE homopolymers; TFE or CTFE polymerized with one or more other fluoromonomers described above such that said other fluoromonomers are  less than 1% by weight of the total polymer (wt. %); TFE or CTFE polymerized with 1 to 99 wt. % of one or more other fluoromonomers, preferably 1 to 50 wt. % of one or more other fluoromonomers, more preferably 1 to 20 wt. % of one or more other fluoromonomers, and most preferably 1 to 10 wt. % of one or more other fluoromonomers. In all cases, the wt. % values refer to the amount of comonomer incorporated in the polymer.
The TFE homopolymers of this invention are not melt fabricable. The copolymers of this invention are melt processible with melt viscosities, determined as described below, of up to 106 Paxc2x7s, preferably in the range 102 to 106 Paxc2x7s, and most preferably in the range 103 to 105 Paxc2x7s. Such fluoropolymers can be glassy, plastic, or elastomeric. They can be amorphous or partially crystalline, melt-fabricable or non-melt-fabricable. The fluoropolymers made by the process of this invention are normally solid at 15xc2x0-20xc2x0 C. and can have any molecular weight (MW) suitable for the intended use. Generally, the weight average MW is at least 50,000 and can range up to much higher values, such as 1,000,000 and even higher.
The identity and proportion in the polymer of units derived from other monomers, fluorinated and fluorine-free, can have wide ranges depending on the physical, chemical, or electrical properties sought. Thus, the polymers of this invention can be plastic or elastomeric, generally according to the identity and proportion of units derived from monomers making up the major part of the polymer composition, as known in the art.
Polymers of this invention can be prepared by any of the known processes for making fluoropolymers. Such processes can be conducted, for example, in an aqueous or non-aqueous liquid medium, the latter including fluorocarbon and chlorofluorocarbon solvents and carbon dioxide, or in mixed media, i.e., hybrid processes, as well known in the art. The olefin, initiator, and chain transfer agent of formula (1) are added to the polymerization medium, i.e. the polymerization medium is not the chain transfer agent. The presence of the chain transfer agent in the polymerization reaction is in addition to the presence of a polymerization medium. The polymerization medium will normally constitute at least 40 wt. % of the polymerization system after polymerization is completed. As is also well known in the art, dispersion or suspension processes can be employed, and polymerization can be conducted in a batch, semi-batch, or continuous process.
Initiators commonly employed in aqueous polymerization of TFE copolymers are water-soluble free-radical initiators such as ammonium persulfate (APS), potassium persulfate (KPS), or disuccinic acid peroxide, or redox systems such as those based on potassium permanganate (KMnO4), or a perfluoroalkyl sulfinate salt plus an oxidizing agent. Such initiators can be used in the process of this invention. Preferred initiators include APS, KPS, and KMnO4.
Initiators for nonaqueous polymerization or polymerization in the solvent phase of a suspension polymerization include perfluoropropionyl peroxide (3P) and (CF3CF2CF2OCF (CF3) COOxe2x80x94)2 (hexafluoropropylene oxide dimer peroxide also known as HFPO dimer peroxide).
Surfactants for aqueous polymerizations include ammonium fluoroalkanoates such as ammonium perfluorooctanoate and 3,3,4,4,5,5,6, 6,7,7,8,8,8,-tridecafluorooctylsulfonic acid, partially neutralized with ammonia.
The chain transfer agents useful in the present invention may be prepared by several processes known to those skilled in the art. A preferred process involves the addition of alcohols to fluorine-containing olefins as illustrated in equation 1. This process is normally carried out in the presence of a catalytic amount of a base such as an alkali metal hydroxide or the alkali metal salt of the alcohol R1OH. This process is discussed by M. Hudlicky in xe2x80x9cChemistry of Organic Fluorine Compoundsxe2x80x9d, 2nd edition, Ellis Horwood, Chichester, UK, 1976, pages 285 to 290 and 407 to 410 and by L. G. Sprague in xe2x80x9cChemistry of Organic Fluorine Compounds IIxe2x80x9d, M. Hudlicky and A. E. Pavlath, editors, American Chemical Society, Washington, DC. 1995, pages 729 to 731.
R1OH+CF2xe2x95x90CF2xe2x86x92R1OCF2CF2Hxe2x80x83xe2x80x83(eq. 1)
Synthesis of the compound CH3OCF2CF2H from methanol and tetrafluoroethylene by this process is disclosed in U.S. Pat. No. 3,609,196. Synthesis of the compound CH3CH2OCF2CF2H from ethanol and tetrafluoroethylene is disclosed in European Patent Application EP 694523.
Chain transfer agents of formula (1) may also be obtained by reaction of fluorine-containing ketones or acid fluorides with an alkali metal fluoride and an alkylating agent of formula R1xe2x88x92L as illustrated in equation 2.
R1xe2x88x92L+MF+C3F7COFxe2x86x92R1OC4F9xe2x80x83xe2x80x83(eq. 2)
wherein R1 has the meaning defined above, L is a leaving group, and M is an alkali metal cation. A leaving group is an atom or group of atoms which, when attached to a primary or secondary carbon atom, is readily displaced by a nucleophile. Typical leaving groups include chloride, bromide, iodide, alkyl sulfates, alkyl sulfonates, arylsulfonates and trifluoromethanesulfonate anions. This process is discussed by A. E. Feiring in xe2x80x9cChemistry of Organic Fluorine Compounds IIxe2x80x9d, M. Hudlicky and A. E. Pavlath, editors, American Chemical Society, Washington, D.C. 1995, page 82.
Chain transfer agent of formula (1) may also be obtained by reaction of a fluorine containing alcohol R2OH with an alkylating agent of formula R1xe2x88x92L. In one example, reaction of 1,1,1,3,3,3-hexafluoro-2-propanol with dimethyl sulfate in the presence of aqueous sodium hydroxide affords a partially fluorinated ether with the formula (CF3)2CHOCH3, as disclosed in U.S. Pat. No. 3,346,448.
Two of the chain transfer agents in the class described by the formula(1), in which R2=perfluoroalkyl, are available commercially from 3M Corporation: Methoxy nonafluorobutane (CH3xe2x80x94Oxe2x80x94C4F9), which is sold as HFE-7100 hydrofluoroether; and ethoxy nonafluorobutane (CH3CH2xe2x80x94Oxe2x80x94C4F9), which is sold as HFE-7200 hydrofluoroether. The use of HFE-7100 and HFE-7200 as polymerization media is disclosed in xe2x80x9cResearch Disclosuresxe2x80x9d, January 1998, p.81, #40576. Similar hydrofluoroethers are also disclosed as polymerization media in U.S. Pat. No. 5,182,342.
Amounts of chain transfer agent used in typical polymerizations range from 0.1-100 parts per thousand (ppt), preferably 1-100 ppt, and more preferably 1-50 ppt. The parts per thousand are based on the total weight of the monomer or monomers fed to the polymerization reaction, i.e. the weight initially charged and subsequently fed to the polymerization vessel in the course of the polymerization. The chain transfer agent may be added during the initial charging of ingredients before polymerization is begun, or it may be added continuously or in portions during polymerization, or during the initial charging and in the course of the polymerization.
Of the chain transfer agents of formula (1), preferred chain transfer agents are those in which a is 2 or 3 and b is 1 or 2. It is believed that the presence of one or two hydrogen atoms in the group R2 increases solubility of the chain transfer agent in water, and therefore chain transfer agents with b=1 or 2 may be especially preferred in aqueous polymerizations. More preferred are those in which R1 has at least two carbon atoms at least one of which is a secondary carbon atom. A secondary carbon atom is one that is bonded to two hydrogen atoms and to two other atoms.
Polymers of this invention contain polymer chains that are terminated with endgroups characteristic of the chain transfer. agents. These endgroups are similar in formula to the chain transfer agent used, the principal difference being that the polymer chain is bonded to a carbon atom of the chain transfer agent that formerly was bonded to a hydrogen.
Relative polymer molecular weights were determined by melt index measurements in which the amount of polymer which flows through a given orifice at a specified time and temperature and under a specific weight is determined. Thus, a higher melt index number corresponds to a lower molecular weight. Melt index tests were run using a Slocomb Model F extrusion plastometer with a 316 stainless steel die 0.947 cm in diameter and with an orifice 0.318 cm long and 0.0794 cm in diameter. The plastometer was heated to 372xc2x0 C. After loading about 2 g of polymer, reinserting the piston and waiting 5 minutes for thermal equilibration, the piston was loaded with dead weight so that the piston and dead weight together totaled 5, 10 or 15 kg. The time required for all or part of the sample to be extruded was measured. The weight of the polymer extruded in one minute is measured. Generally, two or three measurements are averaged and multiplied by 10. The result is reported as melt index in units of g/10 minutes. In some cases in which polymer of very low molecular weight was formed, all or part of the polymer sample extruded from the plastometer during the 5 minute equilibration time. In these cases, the melt index is reported as xe2x80x9chighxe2x80x9d.
The number of unstable end groups was determined by infrared spectroscopy on thin polymer films which were compacted by pressing at room temperature. Peak intensities at about 1775, 1815, 1795 and 1660 cmxe2x88x921 were used to determine xe2x80x94COOH (dimer), xe2x80x94COOH (monomer), xe2x80x94CF=CF2 and xe2x80x94COOxe2x88x92K+ concentrations, respectively. Intensity of a band at about 2365 cmxe2x88x921 was used to correct absorptions for film thickness. The total of xe2x80x94COOH, xe2x80x94CFxe2x95x90CF2 and xe2x80x94COOxe2x88x92K+ groups is reported as number of ends per 106 polymeric carbon atoms (106 C).
Polymer compositions were determined by 19F NMR spectroscopy on melted polymer samples at about 300 to 320xc2x0 C. The amount of hexafluoropropylene incorporated was determined by integration of a signal at about xe2x88x9271 ppm (CF3) versus the total of CF2 absorptions in the region xe2x88x92105 to xe2x88x92130 ppm. The amount of perfluoro (ethyl vinyl ether) incorporated was similarly determined by integration of its CF3 peak at about xe2x88x9288 ppm.